Process of condensing reduction products of acenaphthene-quinone, &amp;c.



Qti'on; oi Acei 'aph t-hene -Qtiin oneand Their, Transfiarmation. into (Endedt}. i

- rather it the acenaphthenequinone.is treat- Kanars n; oremmircif, Gr m-m, A'SSIGNOB, TO THE FIRM oF-KALLE I v & COMPANY, 'AKriEnGEsELLscHArT,gor- BIEBRIGH, GERMANY.

PRDCE'SSTOE @QNDENSING' REDUCTION QPBODUCTS OF -ACENAPH THENE-QUINQNE; 860..

s eetietg-tett rsjratent-J Patented July 26, I afrmino.seem}; f ,a.

saltgare soluble L i nown that LII .xnnEnnnn-koctoi Withelittle alkaliit hisj colorlessb but 3 by and chemist,- subjecti o'f t ;feebly blue-colored saltswhich are-felon King. l.iiuss'ia,;; r'esidiiig =at Biebrich-o ed-, 5 'yfan excessof, alkali, into deep yio' t; the-,B-hine in .the- German Em ire,' ;hairefinz-' blue-colored salts- With. magnesia, ma a? so vented ittain f ne'wfand use uli-I'Iinpim i ,feeblyjcolored or colorless-salt is reduce-d. helieu ,coi'n ound can be crystailig'd out of; al" holj an in theflfornrof vthin.acicular .1 crystals; having -'a mel t'ingfpointilofi 25;

e ut iaden ieflMaii'ufactiirelofNew 'Reducboiling with glacialj'ac'etic 1163 facic acetylization takes lace .With hi3 ,sulfit'e, under the samekon itidris, af-bi'siilfitc'f ,mponnd formed-which is deoinposd by 'a l kalies ,or facidsw This s eco'nd "rducl Product a f iithiclt tlielfollo'uri'ng i 1i" 1 z I 1-. u t .Grueb e and G-feller have {reduced acena'p means of zi'ncdust' and gl t and have thus fobt-ain acenaphthenne- '(tl'nnak n, fvol 276%;189} tlpli pr ductdoes-not' forni'any Incre- 'color p'ag-llgx Tltisjbodyis not napablejof jco i'ng'imntter when combinedwith inddxyllor' densatio with-indoi'ryl or S QXy-I-thi nap ;3-oxyflathionaphthene It "ield s na e: 1 i gcn'eous compounds," the lpnlliral-isalts'yoi thence I, J p v {11 have owtund that new deriYat-ive o acenaphthene'fz or. reduction p'r'qducts"of acenaphthene -quinone are obt'aindlfif. the) reducing actionis not carried, as; far n Graebes and. Gfellers e xpcl' ii bn utgr-hich ,are easily soluble in water, and do I "not; posscssin themsel ye s the characteristics of =coloring mattersy but are ;oasily conv erted into valuable dyesfbybxn ig n a ents e s ad-b the tre: z ---The products, obtained in this manner may be employed in the textile industry for the production of dyes on the fiber. If the dyer .impregnates afabric with an alkaline solution of these products and afterward exposes it to an'oxidizing action, for instance to that of the air, a dye is formed on the fibers. These coloring matters are identical with those formed by the'condensation of acenaphthenequinone with 3-oxyl-thionaphthene or indoxyl. -90

The object of m invention is now to transform acenapht ene-quinone into a reduction roduct and to combine this with 3-oxy-1-thionaphthene or indoxyl and derivatives of either of them formin homogeneous compounds not possessing t e characteristics of coloring matters but yielding such when oxidized on the fiber.

In order to describe the manner-in which my invention ma be carried out I give the 100 following examp e. g

20 kilograms of acenaphtheneuinone, after bein moistened and-groundwith commercial a cohol, are introduced, in small ortions, at a time, during from one to two 105 ours, into a mixture of 2QO kilo rams of iron filings orj'trimmings, 500 iters of water, and 10 kilograms of 50 per cent. acetic acid, the mixture being heated to from to centigiade andwell stirred.

ed with mild reducing agents. 80

The first reduction product, which is referably produced by the action of alkaine reducing agents (such, for instance, as

alkali sulfid, ammonia, or caustic soda lye and zinc dust, grape sugar and caustic soda lye) on acenaphtheiie-quinone, is characterized by the following properties: It is ver difiicultly soluble in water. \Vith alkalies it forms salts which are of a deep blue color and almost insoluble in water. In glacial acetic acid it partially dissolves, acetylization taking place. On heating with aqueous bisulfite, both the free compound and its ditficultly soluble salts are convertedinto a bisulfite compound which is, however, decomposed by both acids and alkalies. The new compound can be crystallized out of ethane tetrachlorid in the form of fine yellowish prisms melting at 248 centigrade.

The compound can be condensed with 3-oxyl-thiona hthene the yield being no homogeneous dy but a mlxture of various products part being coloring matter.

- By reduction in acid, neutral or alkaline media the compound is converted into a second stage reaction product. But the latter may also be produced starting immediately from acenaphthene uinone. The compound so-obtained is so able in water and it forms, with alkalies, two groups of hour until the quinone has entirely disap-* The mixture is kept at the same tempera ture and stirred continuously for another ared. The mixture is then rendered-alkaine by carbonatcof sodium, 150 kilo rams of common salt are then added an the whole is allowed to cool and is filtered. The residue, freed, as far as possible, from the lye,'is extracted withboiling alcohol. The alcoholic extract thus obtained is, after the addition thereto of 15 kilograms of 3,-oxy-1- thionaphthene and 5 kilograms of a 10 er cent. solution of sodium carbonate, boi ed 'for from one to three-hours at the reflux condenser, air being excluded. The alcohol becomes slightl violet and the resulting leuco compoun separates for the greater part in slightly colored crystals. After dis'- tilling of? the alcohol, a reddish product is obtained which dissolves in hot diluted caustic soda lye free from air, a vat liquor, of a red-violet color, being formed.

1131 16 above example describes a process for ma carried out within wide limlts.

.' For'condensation with the reduced prodnot also the derivatives'of 3-oxy-1-thionaphtheme as well as indoxyl and derivatives thereof may be employed.

Now what I claim is: 1.' As a new process the-manufacture of new-condensation products not possessing inthe new roduct, but my invention is not limited to t is example which may be compo themselves the" characteristics of coloring matters from 3-oxy-l-thionaphthene or in-.

doxyl. or derivatives of either of them'on one side and a reduction product of acenaphtheneuinone on the other side, by. treating acenap thene-quinone with mild reducing agents until a water soluble colorless body is formed yielding easily soluble alkali salts,

which are of a violet-blue color, in resence of an excess of caustic alkali, and y condensing this reduction product with indoxyl 3-oxy-1 -thionaphthene or derivat'ves 0 either of them.

2. .As a new product the compound from the reduction product of acenaphthenequinone, which is colorless, soluble in water and yields soluble deep violet-blue-colored alkali salts in presence of an excess of canstic alkali with a molecular quantity-of 3- Witnesses:

\JEAN Gmmn, CARL Gnmgo.

tEierecipitate of- KARL' ELBEL. 

